CN104995264B

CN104995264B - A kind of curable fluid composition

Info

Publication number: CN104995264B
Application number: CN201380065884.2A
Authority: CN
Inventors: G·摩里亚; A·R·米尼汉
Original assignee: PQ Silicas UK Ltd
Current assignee: PQ Silicas UK Ltd
Priority date: 2012-12-19
Filing date: 2013-12-19
Publication date: 2018-05-29
Anticipated expiration: 2033-12-19
Also published as: EP2935471B1; IN2015DN04156A; WO2014096831A1; US10280331B2; BR112015014441A2; CN104995264A; KR20150099520A; GB201222908D0; EP2935471A1; JP6289501B2; PT2935471T; JP2016507609A; ES2666593T3; US20150307735A1

Abstract

The present invention relates to a kind of curable fluid composition, such as alkyd paint or resin, said composition contains through oxidation cross-linked curable adhesive, the oxidation cross-linked drying immunomodulator compounds and delustering agent suitable for being catalyzed described adhesive.It with the surface area measured by BET is 250m that the delustering agent, which is,²Precipitated silica, the precipitation metal silicate of/below g, such as Ca, Mg or Al silicate or their mixture, can substantially be amorphous.Immunomodulator compounds are dried as the transition metal chelate containing ligand, such as the chelate of iron-based or manganese base.Said composition can cure in acceptable time internal oxidition, cured solid, such as coating is made, and with dumb light.

Description

A kind of curable fluid composition

Technical field

The present invention relates to a kind of curable fluid composition, such as alkyd paint (alkyd paints), said compositions Containing by oxidation cross-linked (oxidative cross-linking), such as by being reacted with the oxygen in surrounding air, can consolidate The adhesive of change.Particularly, the present invention relates to a kind of curable fluid composition, transition metal chelate is contained as dry Drying prescription compound (siccative compounds) combines to provide the delustring of dumb light to the composition surface after curing Agent.

Background technology

One of paint, coating of most ancient form are to be based on (being referred to as fixed oil (hardening derived from vegetable oil Oils), for example, linseed) curable adhesive.Such oil is the esters formed by the reaction of aliphatic acid and glycerine： The hydrocarbon end of fat is included in the presence of oxygen or other oxygen donors (such as peroxide), and what can be cross-linked with each other is total to Yoke diene.

Modern, synthesis version this kind of paint is referred to as alkyd paint.Term alkyd (alkyd), which is derived from, to be used for mutually The AL of polyalcohol (polyhydricALcohols) of the reaction generation polyester and CID (changing for KYD) of sour (aCIDs). This, term alkyd and polyester are synonym.In tradition is applied, it is next to include that term alkyd is commonly used to denote the polyester being modified Pendant group of the fatty acid chain of self-hardening oil as polymer chain.

Typical alkyd resin can by by fixed oil (be also referred to as in the prior art and this specification drying oil or Half drier oil of person (semi-drying oils)) such as linseed oil and acid anhydrides and glycerine heat, carried with obtaining from oils The unsaturated pendant group of fatty acid group (refers to C₁₂-C₂₄Hydrocarbon chain) polyester.

It, both can be by alkyd resin in water or aqueous molten for the use in coating, varnish, ink or coating It emulsifies, can also be dissolved in organic solvent in liquid.In order to become apparent, refer to water using term " alkyd paint " in the present specification Base coating (water-based paints) or solvent-based coating (solvent-based paints), varnish, ink, coating etc. Deng they are based on passing through oxidation cross-linked curable alkyd adhesives.Typically, the ambient oxygen from air can provide It is oxidation cross-linked, but as described herein, it can also again additionally or selectively use such as peroxidating of other oxide sources Object.

The desiccation (drying) of alkyd paint can be understood as mechanism can distinguish by two kinds, different and occur.First, The solvent of evaporation composition results in high viscosity, viscous layer.Secondly, the unrighted acid portion of alkyd resin in this layer / occur oxidation cross-linked film to be caused to harden.Both mechanism are referred to alternatively as physics desiccation and chemical desiccation (in this specification Middle the latter also referred to as aoxidizes desiccation or curing) and can simultaneously and/or sequentially occur.The chemical desiccation stage is spontaneous Oxidation process (can describe) typically via radical chain reaction mechanism according to initiating stage, build phase and termination phase It carries out.Many alkyd paints contain drier (siccative agent) using the initiator as this chemical desiccation stage.

Cobalt compound, particularly cobalt soap (cobalt soaps), are widely used as alkyd paint or can be consolidated based on other Change the drier (catalyst triggered as chemical desiccation) of the oxidation desiccation of the coating of resin.In recent years, cobalt toxic and Potential carcinogenicity and it be out of favour in the environment as discarded object, caused in alkyd paint industry from cobalt-based dry Agent is produced and turns to alternative drier.International Patent Application Publication text WO2008/003652 A1 disclose one kind and are used for Air desiccation alcohol acidic group resin and coating, such as the drying of coating, varnish or wood staining ink and malthoid floor covering Agent, based on iron/manganese complex that nitrogen ligand is supplied containing four tooth bases, five tooth bases or six tooth bases.

By oxidation cross-linked curable adhesive, except their applications in coating, can also be taken as be used for it is more The basis of the thermosetting resin of the industrial purpose (such as founding materials, fibre reinforced materials and coating) of kind.

It, can durings not as coating, varnish, ink etc. when curable adhesive to be used to use in structural material To realize and cure by further unsaturated ethylene alkenyl monomer (such as styrene) is added in into resin, to promote to pass through freedom The crosslinking (curing) for the resin that base combined polymerization mechanism is combined with peroxidating class initiator.Again, typically, using cobalt-based chemical combination Object is as drier (primary accelerator (primary accelerator)) with the curing for the alkyd resin for accelerating this curable.Have Alkyd paint is closed as described above, being to make us full with safer and more environmentally acceptable substitute substitution cobalt-based drying immunomodulator compounds Meaning.International Patent Application Publication text W02011/083309 A1 disclose one kind and are provided commonly for peroxide type initiators Help unsaturated polyester resin, vinyl ester resin and the cured accelerating agent of acrylic resin.The accelerating agent of the disclosure is to be based on Three tooth bases, four tooth bases, five tooth bases or six tooth bases supply iron/manganese complex of nitrogen ligand.

Through this specification, term " desiccation " and " curing " are used interchangeably to refer to curable fluid composition by liquid It is converted into the solid-state with the hard surface of solids.

The content of the invention

Synthetic silica (Synthetic silica) is used as to the delustering agent of alkyd paint sometimes.It has now been found that and works as Cobalt-based drier, such as cobalt soap, when being substituted by the drier based on the transition metal chelate containing ligand, in the drying of replacement It shows to interact between agent and the synthetic silica for being traditionally utilized as delustering agent, the effect for hindering drier can be caused Power, the result is that than without longer drying time can be obtained during synthetic silica.In other words, although will be based on containing matches somebody with somebody The drier for displacing cobalt of the transition metal chelate of body is used for gloss paint, but for low luster coating (matt Coating it is problematic) to obtain long drying time.Typically, tradition is used as the synthetic silica of delustering agent with larger Specific surface area and pore volume (pore volume).

Therefore, it is necessary to a kind of delustering agent, be suitable for by oxidation cross-linked cured alkyd paint, thermosetting resin or its He uses in fluid composition, and uses manganese base or iron-based drier, wherein, which will not cause in drier performance not Acceptable loss, and the addition of the delustering agent will not cause the hardening time of unacceptable or mistake to(for) alkyd paint More growths can also provide acceptable extinction effect to eliminate the gloss finish (gloss to cured composition certainly finish)。

The first aspect of the present invention is the provision of a kind of curable fluid composition, and said composition contains：

A) by oxidation cross-linked curable adhesive,

B) be suitable for catalysis described adhesive oxidation cross-linked drying immunomodulator compounds and

C) delustering agent,

It is characterized in that, the dry immunomodulator compounds are for the transition metal chelate containing ligand and the delustering agent：

It is 250m with the surface area measured by BET²/ below g, it is preferably 200m²The precipitated silica of/below g (precipitated silica),

Precipitate metal silicate (precipitated metal silicate) or

Their mixture.

The second aspect of the present invention is to provide application of the following substance as the delustering agent of curable fluid composition：

Precipitated silica, it is 250m to have by the surface area of BET measurements²/ below g, it is preferably 200m²/ below g,

Precipitate metal silicate or

Their mixture,

Wherein, the curable fluid composition contains：

By oxidation cross-linked curable adhesive and

Transition metal chelate containing ligand, as the oxidation cross-linked drier suitable for being catalyzed described adhesive Close object.

Specific embodiment

Through this specification, term " containing " or " comprising " refer to including ingredient is specified still to be not excluded for other compositions In the presence of.Term " mainly by ... form " or " mainly with ... form " refer to including specifying ingredient still eliminate other into Point, except the material occurred as impurity, as providing the inevitable material of the product of the process of ingredient appearance, with And the ingredient for being not configured to the purpose of the technique effect of the acquisition present invention and adding.Typically, mainly by a series of into being grouped into Composition can contain less than 10 weight %, typically less than 5 weight %, more typically less than 1 weight % it is non-designated into Point.

When any suitable, it can also be used to include using term " containing " or " comprising " " main By ... form " or " mainly with ... form " the meaning, and can also be used to include " by ... form " or " with ... form " the meaning.

The solvent or liquid of the water containing 65-100 weight % are referred to for aqueous or water-based solvent or liquid.

Selectable and/or preferred feature discussed below can be used alone, and can also be mutually combined use, It if is suitble to, and particularly to be applied in combination, as described in subsidiary claims.It is described here for The selectable and/or preferred feature of each aspect of the present invention it can be appreciated that other aspects for use in the present invention, Unless significant discomfort is closed.

The first aspect of the present invention provides a kind of curable liquid containing by oxidation cross-linked curable adhesive Body composition.Described adhesive preferably comprises the polyunsaturated fatty acid part (conjugated of conjugation polyunsaturated fatty acid moiety)。

Described adhesive can merely for it is undersaturated oil or acid or can be preferably containing unsaturated group can Crosslinked resin (cross-linkable resin), such as unsaturated polyester (UP), vinyl esters or acrylic resin.Preferably, institute Adhesive is stated as alkyd resin or contains alkyd resin.

The composition of the present invention typically contains the adhesive of about 90 weight % of about 1-, preferably comprises from about about 70 weights of 20- Measure the adhesive of %.

Alkyd resin can by one or more polyalcohols, one or more polybasic carboxylic acids or corresponding acid anhydrides and The polycondensation reaction of long-chain unsaturated fatty acid or oil is made.

Glycerine is suitable for the widely available polyalcohol used in alkyd resin is prepared.Other are suitable polynary The example of alcohol includes：Pentaerythrite, (one shrinks) dipentaerythritol, 1,2- ethylidene glycols, diethylene glycol (DEG), propylene glycol, new penta 2 Alcohol, trimethylolpropane, trimethylolethane, double-(trimethylolpropane), 1,6- hexylene glycols (1,6-hexane diol) etc.. Being suitable for the polybasic carboxylic acid used in alkyd resin is prepared or their corresponding acid anhydrides includes：Phthalic acid and its isomers, 1,2,4-tricarboxylic acid, 1,2,4,5- benzenetetracarboxylic acids, pimelic acid, adipic acid, azelaic acid, decanedioic acid, maleic acid, fumaric acid and tetrahydrochysene are adjacent Phthalic acid (tetra-hydrophthalic acid).To preparing useful suitable drying fatty esters of alkyd resin, half-dried Aliphatic acid or their mixture include olefinic undersaturated (ethylenically unsaturated), conjugation or it is non-common The C of yoke₁₂-C₂₄Carboxylic acid, such as oleic acid (oleic), ricinoleic acid (ricinoleic), linoleic acid (linoleic acid), Asia Numb acid (linolenic acid), licanic acid (licanic) and eleostearic acid (eleostearic acids) or it Mixture.Typically, acid can be to use in the form of being derived from the fatty acid mixt of natural or synthetic oil.Above make With term " half-dried " and " drying fatty esters " with fat of the description derived from half drier oil or drying oil (i.e. fixed oil such as linseed oil) Fat acid.The classification of such oil is based on the iodine number for oil；Its iodine number is suitable for being more than 140 for drying oil.For For so-called half drier oil, iodine number 125-140, and for nondrying oil, iodine number is less than 125.Aliphatic acid can be with By oil hydroxylating and therewith remove glycerine and be made.

When the alkyd resin in alkyd paint in use, alkyd resin typically can by with from surrounding air Oxygen reaction and carry out oxidation cross-linked.This coating (including varnish described herein etc.) is generally applied with relatively thin coating, So that the oxygen in air can be promptly spread in order to provide oxidative cure.

It, can be by using peroxidating when needing to form thicker structure by the curable fluid composition of the present invention Object type initiator cures the curable fluid composition.The curable fluid composition can also include unsaturated ethylene Alkenyl monomer, such as styrene is with the curing for the fluid composition for promoting this curable.When by peroxide rather than from ring When the oxygen of border air is used for oxidation cross-linked, what peroxide initiator can be known to those skilled in the art is suitable for solid Change any peroxide of unsaturated polyester (UP), vinyl esters or acrylic resin.Such peroxide includes organic and nothing The peroxide of machine can be solid or liquid, can also use hydrogen peroxide.The example of suitable peroxide includes：It crosses Carbonate (peroxycarbonates), peroxyester (peroxyesters), dialkyl peroxide etc..Suitable peroxidating Object can be oligomer structure or polymer architecture.Lipid peroxidation ester, liquid hydroperoxide (hydroperoxide) or hydrogen The liquid mixture of peroxide can be particularly useful in the curable fluid composition of the present invention to being mixed into.

The curable fluid composition of the first aspect of the present invention also contains suitable for the oxidation cross-linked of catalyzed adhesive Drying immunomodulator compounds.Dry immunomodulator compounds are the transition metal chelate containing ligand.Term " transition gold used herein Belong to " refer to the element in periodic table of elements d areas, include the element of 3-12 races, thus including zinc, calcium and mercury (mercury) with And group of the lanthanides and actinides.Preferably, the dry immunomodulator compounds are the chelate of manganese, iron or their mixture.So Compound efficiently catalysis oxidation can cure and there is relatively low toxicity.Although the cobalt-based drier based on cobalt soap It closes object to widely use in the prior art, but because the compound has not been preferably to select to the harm of health and environment It selects.The coloring that cobalt compound is also possible to would not want to is introduced on the cured article for coming from curable fluid composition.For this purpose, The fluid composition of the first aspect of the present invention does not preferably contain cobalt compound, the drying immunomodulator compounds including cobalt-based.The present invention Employed in drying immunomodulator compounds for transistion metal compound, and the transition metal can contain the cobalt as impurity. On the basis of the total metal content in the dry immunomodulator compounds, the content of any such cobalt is preferably less than 5 weight %, more preferably Less than 1 weight %, still more preferably less than 0.1 weight %.

Typically, the drying immunomodulator compounds employed in the present invention can effectively catalysis be solid in wider compositing range Change.Therefore, on the basis of the weight of curable fluid composition, the dry immunomodulator compounds are in the present compositions Content is 0.0005-0.1 weight %, such as 0.001-0.05 weight %, then such as 0.002-0.01 weight %.Typically, do Weight (the parts per million of the weight of composition in the composition of the transition metal present invention for the chelating that drying prescription compound is provided (parts per million)) for 0.45-90ppm, such as 0.9-45ppm, then such as 1.8-9ppm.

The curable fluid composition of the first aspect of the present invention also contains delustering agent.Delustering agent is precipitated silica Silicon, precipitation metal silicate or their mixture.The mixture of silica and silicate can be used as delustering agent.It is preferred that Ground, precipitated silica and/or precipitation metal silicate are essentially unbodied.Can be provided using amorphous materials is had Required low surface area, and the material with sufficiently high pore volume, this makes it possible to the extinction effects obtained.

When the delustering agent in the composition of the first aspect of the present invention is or during containing precipitated silica, dioxy is precipitated It is 250m that SiClx, which has by the surface area of BET measurements,²/ below g is preferably 200m²/ below g, more preferably 150m²/ below g, Still more preferably it is 100m²/ below g is most preferably 70m²/ below g.In curable fluid composition, there is larger table The presence of the precipitated silica of area may bring adverse effect to the solidification rate of the composition.Preferably, in this hair It is 10m to be used as the precipitated silica of delustering agent in bright to have by the surface area of BET measurements²/ more than g is, for example, 20m²/ g with On.The delustering agent existing in the form of precipitated silica when with more low surface area, can be shown as delustering agent The effect of reduction, and be failure on the gloss on surface for reducing desiccation/solidification composition filling.

Precipitated silica or the surface area and pore volume for precipitating metal silicate, can pass through Brunauer-Emmett- The standard nitrogen absorption process of Teller (BET) is carried out with 2420 instrument of ASAP that the Micromeritics of USA is provided using multipoint method Measurement.This method and " S.Brunauer, P.H.Emmett and E.Teller, J.Am.Chem.Soc., 60,309 (1938) " Paper be consistent.Before measurement, it is necessary to when sample is placed in vacuum degasification 1 is small at 270 DEG C.Sample cell (is equipped with and removed Sample after gas) analysis station is transferred to, it submerges in liquid nitrogen and measures nitrogen thermoisopleth (nitrogen isotherm).It is in P/Po It fetches in the range of 0.08-0.20 strong point, using BET theoretical calculation surface areas.With adsorption line (the adsorption leg) Upper P/Po is pore volume measured value by recording at 0.98.

Preparation is described in International Patent Application Publication text WO-A-97/02211 has low surface area, is, for example, less than 250m²The typical method of the unbodied precipitated silica of/g.This method includes：It is (such as logical being used for agitation material Cross stirring) mixing vessel in, by the molar ratio (SiO of 17.0-21.5 weight %₂∶Na₂O) the silicate for being 2.1: 1-2.5: 1 Solution is added to the water.Then, the molar ratio for adding 17.0-21.5 weight % is the silicate solutions of 2.1-2.5, while The sulfuric acid solution that 15-20 weight % is added in the period of 80 minutes was preferably less than more than 40 minutes, the flow velocity used causes PH value is maintained in the range of 8.0-9.0, is mixed to be provided with solution/slurries of stirring or agitation gained and is made the solid of precipitation Suspended state is kept in slurries.Then by gained slurries at 90 DEG C -100 DEG C of temperature aging 0-30 minutes, preferably 8-12 points Clock.Then the sulfuric acid solution of second of addition 15-20 weight % is carried out so that pH value is down to pH 3-5.Gained slurries are in 90- Further aging 0-20 minutes, preferably 8-12 minutes between 100 DEG C.PH to pH 3.5-5 is finally adjusted, filtering slurries, washing are simultaneously It is dry.

This is an example of suitable method, has in WO-A-97/02211 and is more discussed in detail.It may be employed His suitable method, can also when needed be improved the above method, molten for example with the silicate of different molar ratios Liquid, such as up to 3.5: 1.

It may then pass through using traditional technology, such as hammer grinding, jet grinding, air-flow crushing (fluid Energy milling) etc., and the subsidiary classification such as air classification (air classification) selectively carried out, it will The unbodied precipitated silica of washing and drying crushes and is classified to provide required particle size range.

The amorphous silica of precipitation, such as available for the delustring for being prepared as using in the first aspect of the present invention Agent, such as in order to prepare delustering agent or be used in the present invention as the basis being crushed and classified, it can be public from supplier such as PQ Department is commercially available.Representative suitable material isAC39 is gone out as the grinding agent in toothpaste It sells.

When the delustering agent of the present invention is precipitates metal silicate, which is the metal of 2-13 races in the periodic table of elements (one or more metals) sinks although the precipitation metal silicate can also contain alkali metal (i.e. the 1st race's metal) as it The by-product in shallow lake.

When the one or more in the metal that the metal is the 2nd race, the metal in the metal silicate preferably selects From calcium, magnesium or their mixing.It is highly preferred that the metal in the metal silicate from the 2nd race is magnesium.When the metal comes from During 12 race, the metal silicate is preferably zinc.When the metal comes from 13 race, the metal silicate is preferably Aluminium.

The typical method that preparation is suitable for the amorphous metal silicates used in the present invention as delustering agent is as follows：

By the aqueous solution of a certain amount of alkali silicate, typically with SiO₂∶M₂The molar ratio of O is 2.0: 1-3.5: 1 Scope, wherein M is alkali metal (be usually Na, K or their mixing), a certain amount of water-soluble metal salt solution (example Such as chloride, sulfate or nitrate) and optional a certain amount of inorganic acid (if such as hydrochloric acid, nitric acid or sulfuric acid-need If reducing pH) it is mixed together in the reaction vessel with agitation such as stirring, to form reactant aqueous solution mixture.Example Such as, when adopting using calcium or magnesium as metal, when just not using acid, and using aluminium as metal, acid can be added in accelerate to precipitate.Typically, Alkali metal silicate solutions, any inorganic acid solution and metal salt solution are fed to mixing together according to required molar ratio to hold In device, with given pace so that the pH of reaction mixture is held essentially constant and is the numerical value in the range of 8-12, sufficiently to stir It is dynamic that the solid of precipitation is made to keep suspended state in gained slurries.During silicate, inorganic acid and metal salt is added in, reaction is mixed The temperature for closing object is maintained at about 30-90 DEG C (being 50-90 DEG C in the case of for example with calcium).So that these into subassembly to obtain The duration of reaction mixture is typically about 15-25 minutes.

Then the solid (metal silicate) of precipitation is isolated from the liquid component of the reaction mixture of gained, for example, it is logical Filtering, and solid is washed and dried.The reaction process may be employed gap method (batch process) carry out or Person is carried out using continuity method (continuous process), wherein by reaction mixture with total addition rate with input solution Identical rate is removed from reaction vessel.For the reaction mixture of such continuity method or batch process, silica it is dense Degree is typically the about 3-10 weight % of the reaction mixture.

It may then pass through using traditional technology, such as hammer grinding, jet grinding, air-flow crushing etc., and incidentally may be used The classification such as air classification (air classification) carried out is selected, it will washing and dry unbodied precipitation metal Silicate solid crushes and is classified to provide required particle size range.

Metal silicate is precipitated, is suitable as preparing the basis being crushed and classified of delustering agent used in the present invention, It can be provided from such as Pq Corp. of supplier and be used as powder stream auxiliary agent (powder flow aids) or inert liquid carrier (inert Liquid carriers) product it is commercially available.These are solids, for example, trade nameAmorphous sediment silicon Sour aluminium andAmorphous sediment calcium silicates.

Obviously the precipitation metal silicate used in the present invention may not necessarily be the precipitated metal in stoichiometry.The precipitation It is regarded as reaction between silicic acid and metal salt and generates precipitation metal silicate and acid.However, the silicic acid as silica Co-precipitation (such as closely co-melting conjunction (co-mingled) in the structure of co-precipitate) with metal silicate is also one kind Selection, such as generate co-precipitate by regarding acid and metal salt combination as reactant with alkali metal silicate solutions reaction. For clarity, it should be understood that term " precipitation metal silicate " means with M_xO/SiO₂Molar ratio be more than 0.05 it is heavy Starch, wherein M represent the one or more in the metal of the 2-13 races selected from the periodic table of elements, and M_xO is precipitated silicate The stoichiometric equation of middle metal oxide, and x is equal to 2/v, v is the chemical valence of metal M.

Term " precipitated silica " is referred to M_xO/SiO₂Molar ratio be sediment less than 0.05, wherein M tables Show the one or more in the metal of the 2-13 races selected from the periodic table of elements.

When the delustering agent in the composition of the first aspect of the present invention be or containing precipitation metal silicate when, to precipitation There is no particular limitation for the surface area of metal silicate, as long as it is effective.It is preferable, however, that the precipitation metal metasilicate It is 450m that salt, which has by the surface area of BET measurements,²/ below g, more preferably 400m²/ below g is still more preferably 250m²/g Below.In particularly preferred embodiments, it is 200m that the precipitation metal silicate, which has by the surface area of BET measurements,²/g Hereinafter, it is preferably 100m²/ below g is most preferably 70m²/ below g.Preferably, in the present invention the precipitation gold as delustering agent It is 10m to belong to the surface area that silicate is measured by BET²/ more than g, such as 20m²/ more than g.Precipitate the delustring of metal metasilicate salt form Agent when with more low surface area, can show the effect reduced as delustering agent, and reduce desiccation/solidification composition filling Surface gloss on be failure.

Being suitable for the invention delustering agent can also be characterized by using the oil absorption of linseed oil.Suitable delustering agent The oil absorption that can show is 80-400g/100g.The oil absorption can pass through ASTM blade wears method (ASTM spatula rub- Out method, U.S. material and test association criterion D281) it measures.The linseed oil used in the test is Fisher Linseed crude oil (the density about 0.93g/cm that Scientific (UK) is provided³, general grade).

The test based on principle be to mix linseed oil with the solid specified, by using scraper on slippery surfaces Abrasion will not destroy or the lotion (putty-like of separated hard putty sample until foring when being cut with scraper paste).Then oil volume used is brought into below equation：

Oil absorption (oil absorption value)=(oil suction grams × 100)/(grams of silica)

Oil absorption is expressed as g/100g.In order to provide preferable extinction performance, for delustering agent, oil absorption can be More than 100g/100g.

Glossiness is coated in Leneta^TMIt is surveyed on the coating or varnish of desiccation on card using BYK Multigloss Amount instrument measures under 60 degree (60degrees).

In order to provide the photoextinction that matte surface will not be caused excessive coarsening, the grain size of the delustering agent be it is preferred, so For the delustering agent by the D of light scattering measurement₅₀(diameter of 50 weight % particles is less than D for average grain diameter₅₀) it is 3-15 μm. Suitably, for the delustering agent, D₉₀(diameter of 90 weight % particles is less than D to value₉₀) it is not more than 30 μm.

The grain size of precipitation metal metasilicate salt particle is suitble to measure using laser diffraction, using Malvern 200 types of Mastersizer, 2000 software v 5.60 of Malvern Mastersizer and Hydro-G dispersal devices.By The device of Malvern instruments (Malvern Instruments, Malvern, Worcestershire) manufacture utilizes Mie theory (Mie theory) calculates particle diameter distribution.It is assumed that the refractive index of scattering ingredient silica is 1.46, and assume to absorb ingredient It is 1.0.The refractive index of water is appointed as 1.33.

Before measuring by sample with the setting of 50% powder in water ultrasonic disperse 2.5 minutes to form dim degree (obscuration) aqueous dispersion for being 15-25%.Pump speed is arranged to 50% (1250+/- 20r.p.m.) and stirring speed Degree is also configured as 50% (500+/- 5r.p.m.).The He/Ne laser (wavelength 632.6nm) of low-power 2-5mW is passed through and is equipped with The fluid chamber (flow cell) of scattered particle in deionized water.Also using blue-light source (wavelength 486nm) come intensifier pair The susceptibility of fine particle.Measurement scattering optical density (scattered light intensity) as angle function and Apparent particle diameter distribution is calculated using the data, wherein the residue of the Michaelis model (Mie model) of fitting initial data (residual) it is less than 1%.It is assumed that the density of particle is constant, it is easy to which the data generated from device obtain above-mentioned or following any The volume and weight percentage of specific dimensions material.In the present specification, it is assumed that density is constant, and grain diameter measurement is weighted using quality Method (weight based particle size measures) or when not assuming that density, can be used the survey of volume weighting grain size Amount method (volume-based particle size measures) represents.

Suitably, in curable fluid composition, on the basis of the total amount of the composition, the nothing as delustering agent The precipitation metal silicate or unbodied precipitated silica of setting may have 2 weight %-15 weight %, be preferably 3 weights Measure %-10 weight %, with this not significantly extend hardening time under sufficient photoextinction is provided.

Typically, delustering agent of the invention can have 2.0cm³The pore volume of/below g is, for example, 1.5cm³/ below g, Or even 1.3cm³/ below g.Method as described above can be used in the measurement of pore volume.The delustering agent used in the present invention Pore volume preferably be 0.1cm³/ more than g.Lower hole body product value may cause photoextinction to be weakened.

The surface area of the delustering agent is preferably 70m²/ below g.Have found when used dry immunomodulator compounds be containing During the transition metal chelate of ligand, the chelate of especially such iron or manganese has the delustering agent pair of these characteristics In in the delustring clear coat composition containing higher alkyd resin content (such as more than 50 weight %) in use, especially effectively.

Preferably, the delustering agent is to precipitate metal silicate, such as unbodied precipitation metal silicate, wherein metal M is the one or more in the metal of the 2-13 races of the periodic table of elements, and wherein M_xO/SiO₂Molar ratio be more than 0.05. It is highly preferred that the metal M of the silicate is selected from aluminium, calcium, magnesium, zinc or their mixture.Even further preferably, the silicon The metal M of hydrochlorate is selected from aluminium, calcium, magnesium and their mixture, is most preferably aluminium or magnesium.It has found compared to no delustering agent The hardening time of equal amounts of compositions, metal silicate, metal silicate particularly preferably provide required low surface area With the delustering agent of appropriate pore volume, and excellent delustring quality is had both, and also have few composition hardening time concurrently to extend.Institute So i.e. M can be suitable for by stating precipitated silicate_xO∶SiO₂Molar ratio be about 0.05-0.6, wherein M_xO is in precipitated silicate The stoichiometric equation of metal oxide, and x is equal to 2/v, and v is the chemical valence of metal.In a kind of particularly preferred embodiment In, when metal M is calcium or magnesium, M_xO∶SiO₂Molar ratio can be 0.05-0.6, be, for example, 0.1-0.4, be, for example, 0.2- 0.3, wherein for M=Ca or M=Mg, x=1 and v=2.In another particularly preferred embodiment, when metal M is aluminium When, Al₂O₃∶SiO₂Molar ratio can be 0.017-0.2, be equivalent to M_xO∶SiO₂Molar ratio can be 0.05-0.6, such as It is, for example, 0.09-0.4 for 0.07-0.5, and M=A1 and x=2/3.

Because the presence of the amorphous colloid or unbodied precipitated silica of high surface area can be to the group of the present invention Close object solidification rate have harmful effect, it is therefore preferred to the present invention curable fluid composition contain 0.1 weight % with Under (i.e. 0-0.1 weight %) amorphous silica, by BET measurement surface area be more than 250m²/g.It is highly preferred that this The composition of invention is not contained is more than 250m by the surface area of BET measurements²The amorphous silica of/g.When the delustering agent is When precipitating metal silicate, preferably unbodied, composition of the invention contains any amorphous two below 0.1 weight % Silica can preferably not contain any amorphous silica.

In another preferred embodiment, the surface area of the delustering agent can be 70m²/ below g, and it is described Curable fluid composition can not contain or the surface area by BET measurements containing below 0.1 weight % is more than 70m²/g Amorphous silica.When the delustering agent is unbodied precipitation metal silicate, which is particularly useful 's.

As routine in the practice of formulation for coating material, silica or silicate delustering agent can be applied waxing to improve Compatibility in delustering agent and the formulation for coating material between other compositions.When using the delustering agent of waxing, with the total of the delustering agent On the basis of weight, wax content is typically at least 1 weight % and can be as high as about 25 weight %, it is preferable that wax content is height To about 20 weight %, more preferably up to about 15 weight %, the most preferably up to wax of about 10 weight %.It is coated with the suitable of delustering agent Wax includes polyethylene wax, microwax (being made by vaseline) or similar.

Silica can be handled in the method for any offer product with wax, and wherein silica is by reasonably uniform Ground is coated with wax.Preferred method includes silica and wax are passed through to the device of size reduction simultaneously, such as pulverizer or aeropulverizer. In a kind of preferred method, before wax and silica are added to pulverizer or grinding machine, by traditional mixer Wax and silica are thoroughly mixed by mixing in proper proportions.Alternatively, wax and silica are distinguished at a suitable rate It is added in pulverizer or grinding machine.The operating condition of fixed grinding machine with ensure when the mixture of silica and wax through pulverizer or During grinding machine, the mixture of silica and wax can reach the temperature higher than wax fusing point.It can be in crushing or process of lapping The size of silica is reduced so that treated silica, which has, is suitable for its grain size used as delustering agent, grain Footpath is usually in the range of the restriction being described above.

In order to which the drying immunomodulator compounds used in the present compositions are the transition metal chelate containing ligand. Compound as it was found that as in paint industry and Resin Industry conventional use of soap base cobalt drying immunomodulator compounds for The drying immunomodulator compounds of replacement are particularly effective.

The ligand can be selected from bidentate ligand, tridentate ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or they Mixture.Particularly, the ligand can be for nitrogen ligand.Specially suitable ligand is included selected from double loop coil ligands (bispidon ligand), N4Py ligands, TACN ligands, three loop coil ligands (trispicen ligand), Macrocyclic polyamine ligand (cyclen ligand) or bridge ligand (cross-bridged ligand).

Preferably, the dry immunomodulator compounds are iron-based or manganese backbone drying prescription compound.Iron ion can be selected from Fe (II) Mn (II), Mn (III) and Mn (IV) can be selected from Fe (III) and manganese ion.

The ligand can be existed by the one or more in following form：[MnLCl₂]、[FeLCl₂]、[FeLCl]Cl、 [FeL(H₂O)](PF₆)₂、[FeL]Cl₂、[FeLCl]PF₆[FeL (H₂O)](BF₄)₂, wherein L represents ligand.

The specific example of immunomodulator compounds is suitably dried as described in WO 2008/003652, including：

By the dimethyl 2 prepared described in WO-A-02/48301,4- is double-(2- pyridyl groups) -3- methyl -7- (pyridine - 2- bases-methyl) -3,7- diazas-bicyclic [3.3.1] nonyl- 9- ketone -1,5- dicarboxylic acids (Dimethyl 2,4-di- (2- Pyridyl) -3-methyl-7- (pyridin-2-ylmethyl) -3,7-diaza-bicyclo [3.3.1] nonan-9-one- 1,5-dicarboxylate) (N2py3o-Cl) and its iron (II) complex compound [Fe (N2py3o-Cl) Cl] Cl.

By the dimethyl 2 prepared described in WO 2005/042532,4- is double-(2- pyridyl groups) -3- octyl groups -7- (pyridine - 2- bases-methyl) -3,7- diazas-bicyclic [3.3.1] nonyl- 9- ketone -1,5- dicarboxylic acids (Dimethyl 2,4-di- (2- Pyridyl) -3-octyl-7- (pyridin-2-ylmethyl) -3,7-diaza-bicyclo [3.3.1] nonan-9-one- 1,5-dicarboxylate) (N2py3o-C8) and dimethyl 2,4- pairs-(2- pyridyl groups) -3- octadecyls -7- (pyridine -2- Base-methyl) -3,7- diazas-bicyclic [3.3.1] nonyl- 9- ketone -1,5- dicarboxylic acids (Dimethyl 2,4-di- (2- Pyridyl) -3-octadecyl-7- (pyridin-2-ylmethyl) -3,7-diaza-bicyclo [3.3.1] nonan-9- One-1,5-dicarboxylate) (N2py3o-C18) and corresponding iron complex, [Fe (N2py3o-C8) Cl] Cl and [Fe (N2py3o-C18)Cl]Cl。

By the N prepared described in EP0765381, N- bis- (pyridine -2- bases-methyl)-two (pyridine -2- bases) methylamine (N, N-bis (pyridin-2-yl-methyl)-bis (pyridin-2-yl) methylamine), it is referred to as N4Py and corresponds to Iron (II) complex compound, [Fe (N4py) Cl] Cl.

By the N prepared described in EP0909809, N- bis- (pyridine -2- bases-methyl-1,1- bis- (pyridine -2- bases) -1- second (N, N-bis (pyridin-2-yl-methyl-1,1-bis (pyridin-2-yl) -1-aminoethane), are referred to as amine MeN4Py and corresponding iron (II) complex compound, [Fe (MeN4py) Cl] Cl.

By WO98/39098 and J.Am.Chem.Soc, 4, the 11- dimethyl that is prepared described in 122,2512 (2000)- Isosorbide-5-Nitrae, 8,11- tetra- azabicyclo [6.6.2] hexadecanes (4,11-dimethyl-1,4,8,11-tetraazabicyclo [6.6.2] hexadecane), it is referred to as Bcyclam and corresponding manganese (II) complex compound, [Mn (Bcyclam) Cl₂]。

By according to document (.J.Chem.Soc, Dalton such as Bernal, J. Trans.1995,3667) and GB2386615 Method synthesis-three loop coil of N- methyl (N-methyl-trispicen) (Metrispicen) ,-three loop coil (N- of N- octyl groups Octyl-trispicen) (C8-trispicen) ,-three loop coil of N- octadecyls (N-octadecyl-trispicen) (C18- trispicen).Corresponding iron (II) complex compound, [Fe (Metrispicen) Cl] Cl, [Fe (C8-trispicen) Cl] Cl and [Fe (C18-trispicen) Cl] Cl, may be employed and the method for MeN4py analogs described in EP-A-0909809 Similarly prepare.

Isosorbide-5-Nitrae-two (quinoline -2- bases-methyl) -7- ethyls-Isosorbide-5-Nitrae, tri- nitrogen of 7- are prepared as disclosed in EP-A-1259522 Ononane (Isosorbide-5-Nitrae-bis (quinolin-2-ylmethyl) -7-ethyl-1,4,7-triazacyclononane) (Quin₂) and corresponding [Fe (Quin TACN₂TACN)Cl]ClO₄Compound.Mn₂([mu]-O)₃(Isosorbide-5-Nitrae, 7- trimethyls-Isosorbide-5-Nitrae, 7- 7-triazacyclononane)₂]PF₆)₂(Mn₂([mu]-O)₃(Isosorbide-5-Nitrae, 7-trimethyl-1,4,7-triazacyclononane)₂] PF₆)₂) can be by J.Chem.Soc, Dalton Trans, the preparation delivered in 353 (1996).

It is suitable for the suitable and commercially available dry immunomodulator compounds being used in the present inventionOxy-coat 1101, which provided as the iron chelate containing ligand.The drying immunomodulator compounds are provided as 1% aqueous solution, with The weight percent that the GOLD FROM PLATING SOLUTION belongs to represents that total Fe contents are 0.09%.

It is Nuodex DryCoat that another kind, which is suitable for the commercially available dry immunomodulator compounds being used in the present invention, (Rockwood), which provided as the manganic chelates containing ligand.The drying immunomodulator compounds are provided as 8% kerosene Solution represents total Mn contents as 1% using the weight percent that the GOLD FROM PLATING SOLUTION belongs to.

It is WorleeAdd 2500 that others, which are suitable for the commercially available dry immunomodulator compounds being used in the present invention, (Worlee), Borchers Dry 0133, Borchers Dry 0246 and 0410 (OMG of Borchers Dry Borchers), these are provided as the manganic chelates containing ligand；And Mordry 410/20 (Delta), Nouryact (Akzo Nobel) and Drycat 408 (Dura Chemicals).

The curable fluid composition of the present invention can be for example water based paint, such as latex paint (emulsion Paint) or dispersing coating (dispersion paint) (continuous phase is formed with water or aqueous solution), solvent based coating (with Non-aqueous solvent is as continuous phase), varnish, wood stain or ink.

Typically, there may also be other ingredients for curable fluid composition of the invention.In order to the present invention's Composition uses, and suitable organic solvent includes aliphatic hydrocarbon, alicyclic and aromatic hydrocarbon, alcohol ether, alcohol ester and N-Methyl pyrrolidone. In addition, the composition of the present invention can also be the form of emulsion, (can be dissolved in organic by the alkyd resin for carrying emulsion form In solvent) aqueous solvent (aqueous solvent refers to the solvent containing at least water of 65 weight %).Typically, with the group of the present invention On the basis of the weight for closing object, the content of solvent is more than 10 weight %.Can use suitable emulsifier well known in the art with Stable emulsion is provided.

The composition of the present invention can contain one or more other compositions, selected from colorant (colourants), pigment (pigments), rust resisting pigment (anti-corrosive pigments), filler (extenders), dyestuff (dyes), increasing Mould agent, surface control agent (surface-controlling agents), so-called dry agent (through-drying Agents), anti skinning agent (anti-skinning agents), antifoaming agent, rheology control agent (rheological Controlling agents), UV absorbers (ultraviolet absorbers) etc..Dry agent is that purpose is to change thoroughly The compound of kind desiccation behavior is, for example, calcium base or Zirconium-base catalyst compound.What the other compositions stated in this section occurred Amount typically reaches 5 weight % of the composition of the present invention, except pigment or filler can reach higher level, such as Up to 20 weight %, even more high.Pigment is UV and to facilitate curing for providing color and opacity or can also absorb The structural strength of composition afterwards.Filler is the mineralogical composition that can also include, in order to save cost instead of any TiO as opacifier₂Part, improve application performance, as the further reduced gloss of delustering agent, inhibit pigmentation or Person preferably solves in order to which the cost of post-coatings provides.Common filler includes such as calcium carbonate, talcum, barite, kaolinite The minerals such as soil, mica.

The composition of the present invention, such as varnish based composition, can by or mainly by following material composition： Foregoing solvent, adhesive, dry immunomodulator compounds, delustering agent.

Conventional hybrid technology as well known to those skilled in the art may be employed to carry out the composition of the present invention Mixing.The delustering agent can add in during the composition of the present invention is prepared at any suitable moment.

The second aspect of the present invention provides a kind of precipitated silicate, and (it is 250m to have by the surface area of BET measurements²/ g with Under, it is preferably 200m²/ below g, more preferably 150m²/ below g, even more preferably 100m²/ below g and be most preferably 70m²/ below g), the application as the delustering agent of curable fluid composition of precipitation metal silicate or their mixture, The fluid composition contains through oxidation cross-linked curable adhesive and is used as the oxidation for being suitable for being catalyzed described adhesive The transition metal chelate containing ligand of crosslinked dry immunomodulator compounds.When disappearing in the composition in second aspect of the present invention Photo etching be or containing precipitation metal silicate when, preferably the silicate have by BET measurement surface area be preferably 450m²/g Hereinafter, it is more preferably 400m²/ below g, even more preferably 250m²/ below g.In a kind of particularly preferred embodiment, institute It is 200m to state precipitation metal silicate to have by the surface area of BET measurements²/ below g is preferably 100m²/ below g, most preferably 70m²/ below g.

The application of the second aspect of the present invention be in order to produce the composition after the curing with matte surface, and compared to Time needed for the curing of other identical curable fluid compositions of delustering agent not using the present invention, which will not The time needed for the curing of curable fluid composition is needed too to extend.

For the preferred feature recorded in the first aspect of the present invention, i.e., with described adhesive, dry immunomodulator compounds and heavy The related feature of shallow lake metal silicate, is all equally applicable in the application of the second aspect of the present invention.For example, the delustering agent It is preferably unbodied.When the delustering agent for the second aspect of the present invention is precipitates metal silicate, silicon is preferably selected from Sour aluminium, calcium silicates or their mixture, more preferably alumina silicate.

When adhesive is or is water based paint containing alkyd resin and curable fluid composition, such as latex paint Or when dispersion paint, solvent-based coating, varnish, wood stain or ink, the second aspect of the present invention is particularly suitable.

It is 70m to have surface area in the delustering agent²/ below g, and the curable fluid composition do not contain or The surface area by BET measurements that has containing below 1 weight % is more than 70m²In the case of the amorphous silica of/g, this hair The application of bright second aspect is particularly conducive to provide rapid curing and excellent delustring.The special peace of the second aspect of the present invention Row be particularly suited for production with matte surface cure after composition, and compared to delustering agent not using the present invention its Time needed for the curing of its identical curable fluid composition, the application not may require that curable fluid composition Time needed for curing too extends.When the delustering agent is foregoing amorphous sediment metal silicate, according to the present invention The application will be particularly advantageous.

When the dry immunomodulator compounds are containing for nitrogen ligand (as bidentate ligand, tridentate ligand, tetradentate ligands, five teeth Ligand or sexadentate ligand or their mixture) iron-based or during manganese base chelate, the application of the second aspect of the present invention is also To preventing excessively increasing for hardening time especially effective.

The present logical embodiment with reference to unrestricted meaning is next, and the present invention is further explained.

Embodiment

A.P. represents " unbodied precipitation " in following table.

Table 1 gives for a series of delustering agents according to the present invention and the table measured by BET for comparing delustering agent Area and pore volume and the linseed oil absorption value (Linseed Oil Absorption values) measured as previously described. In table 1, metal silicate according to the present invention is represented as 1i-7i, and (for the ease of comparison, " i " refers to " present invention (invention) "), silica according to the present invention is expressed as 8i.Silica 9c-12c is then that (" c " is referred to comparative example " comparison (comparison) ").

Using fluid energy mill machine/clasfficiator, by delustering agent A.P. alumina silicate R, A.P. alumina silicate P W1, the A.P. silicon in table 1 Sour aluminium P W2, A.P. calcium silicates Q, A.P. silica C, A.P. silica D, silica gel X, silica gel Y (be respectively 2i, 3i, 4i, 5i, 9c, 10c, 11c and 12c) it is ground to the grain size that each is suitable for delustering agent.Other delustering agents are with them " when being made The form of (as produced) " uses, their grain size is also given in table 1.

Delustering agent A.p. alumina silicate P W1, A.P. alumina silicate P W2 and silica gel Y (being respectively 3i, 4i and 12c) is Wax-coated. A.P. alumina silicate P W1 have wax content be 10% hard polyethylene wax (hard polyethylene wax) (with the amount of silicate On the basis of), A.P. alumina silicate P W2 have the microwax that the microwax that wax content is 15% and silica gel Y have wax content to be 12%.

Embodiment 1

First Series experiment in, using delustering agent set forth below come prepare provided in table 2 in air-cured varnish Matte varnish in composition.

Machine (wired hand coater) or applicator (block are applied using K- sticks (K-bar), wired hand Applicator the varnish of 100 μm of wet-film thickness) is applied.

Varnish after all desiccation all provides sufficient matte effect, except not plus delustering agent composition there is provided Gloss.

For each composition containing delustering agent, the content added in is the 5% of composition weight.

Table 2- clear coat compositions

¹(parts by weight of addition refer to the commercially available ingredient for including solvents/carriers)

The content of Oxy-coat 1101 corresponds to the Complexing Iron for containing 3.7ppm (parts per million) in composition.

Table 3 and 4 gives the time for reaching the various desiccation stages needed for composition.It is surveyed manually by the touch of hand These fixed times, using the desiccation stage as described below：

It is-viscous=to touch tacky.Touch can leave apparent trace, and majority of case lower surface can be left permanent damage Mistake/damage.Mobile finger can leave apparent drag mark.

- SI. glues=touches somewhat tacky.Touch hardly leaves trace, and will not cause permanent damage.It is mobile Finger can leave a small amount of drag mark.

- V.SI. glues=has touched very slight tacky.Touch will not realize there is trace, but touch-surface and non-dry 's.

It is-dry=not glue.

In table 3, drying time is measured under room temperature (25 DEG C) and obtained, and low temperature (9 DEG C) desiccation condition is used in table 4, because This drying time is longer.

For the bright varnish (gloss varnish) of no delustering agent, when entire drying time is respectively 8 small (RT) and 16 it is small when (low temperature).

Comparison delustering agent A.P. silica C, A.P. silica D and silica gel X are added in into varnish base fluid (is respectively 9c, 10c and 11) cause drying time increase RT be issued to 55 it is small when, when during low temperature being more than 60 small.When 60 hours not yet Reach desiccation, with regard to no longer further being measured in these experiments.

Table 3- varnish RT desiccation

Table 4- varnish low temperature desiccation

It is most for delustering agent A.P. alumina silicate P, A.P. calcium silicates Q and A.P. silica A (being respectively 1i, 5i and 8i) Pipe is more much longer than the drying time for bright varnish for RT desiccation, but compared with silica A.P. silica C, A.P. in this system, these delustering agents are shortening the dry of RT desiccation by silica D and silica gel X (being respectively 9c, 10c and 11c) Change and give sizable improvement on the time.

For low temperature desiccation (9 DEG C), only A.P. alumina silicate P samples (1i) give the desiccation in when 60 is small, for sample Product A.P. calcium silicates Q and A.P. silica A (be respectively 5i and 8i) only when 60 is small in a period of reach V.SI. and glue.

In short, it is used in the results show of varnish such as described delustering agent substitute composition in detail in the claims Make the useful part of the silica of traditional high surface area of delustering agent, as the drier (cobalt based on cobalt soap Soap-based siccative agents) substitute.

When using the content for adding in 5% in clear coat composition based on the drier of cobalt soap to provide extinction effect, hair Now not only according to the present invention delustering agent, A.P. alumina silicate P, A.P. calcium silicates Q and A.P. silica A (be respectively 1i, 5i and 8i), and the unbodied delustering agent of high surface area silica such as A.P. silica C, A.P. silica D for comparing With silica gel X (being respectively 9c, 10c and 11c), any significant delay of drying time will not be all caused.This can pass through preparation Essentially identical clear coat composition confirms with the varnish in table 2, but unlike, using Octasoligen^TM Cobalt (being provided by OMG Borchers) substitutesOxy-coat dries immunomodulator compounds.In this case, for being with or without The composition drying time of delustering agent is the same, and be at room temperature when 5-8 is small in the range of, it is small in 10-20 under low temperature When in the range of.

Embodiment 2

By delustering agent being added in the base composition identified in the following table 5 (base composition) prepare sky Curing coating composition.Disappearing with being included in base composition of providing of %w/w is shown in following table 6 and 7 The addition content of photo etching.The delustering agent for being used to prepare each air curing coating composition is as follows：

The coating of machine or applicator using 100 μm of wet-film thickness is applied using K- sticks, wired hand.

Table 5- base compositions

¹(add in parts by weight and refer to the commercially available ingredient for including solvents/carriers)

Reach the time needed for each stage of desiccation to each coating composition by using B.K. drying machine methods of testing (ASTM D5895-13) and Braive loggers (Sheen Instrument Ltd. (Sheen Instruments Ltd)) measure. These measurements, which include drawing red needle with the speed of 24.4mm/h, crosses desiccation coating and track/marking is formed in coating.When After coating desiccation, it is observed that the different markings, and gradable is following desiccation stages：

- concentrate on contact site=coating and will not flow back into the track left by pin, pyriform recess can be formed in coating；

- not viscous=coating surface starts desiccation, and pin scratches the coating surface；

- stiff=coating starts to parch, and pin leaves the marking in coating surface；And

- parching=does not form the marking.

Table 6 below, which gives, to be reached the desiccation stage for the coating of above-mentioned each series and starts the required time.With each The delustering agent used for preparing the coating composition shows each coating composition in example.Painting prepared by other delustering agents useless Material is shown as " no silica ".In table 6, drying time measures under RT (25 DEG C).Experiment terminates when 24 is small.

In some examples, track is not evident that each desiccation stage.This is specified in following table 6. In some examples, test carry out 24 it is small when during do not reach the desiccation stage.This is also referred in following table 6 It is bright.

Under cryogenic apparent desiccation is observed for most of samples are not interior when 24 is small.In order to obtain low Further data under the conditions of warm desiccation, using the method (touch-drying of touch-desiccation described in embodiment 1 Method) further tested under the conditions of low temperature desiccation.The experiment is terminated when 48 is small.It is given in table 7 below pair Reach each time touched needed for the desiccation stage in measuring composition at 9 DEG C using touch drying method.

It is surveyed on coated in the desiccation coating or varnish on LenetaTM cards under 60 degree using BYK Multigloss instrument The glossiness of each coating composition after determining desiccation 14 days, and be recorded in the following table 6 and 7.

Table 7- coating low temperature desiccation (touching test method)

In the B.K. drying machine test methods of RT (25 DEG C) desiccation, with the painting of A.P. magnesium silicate S delustering agents (6i) preparation Material has most fast drying time.

In the B.K. drying machine test methods of RT (25 DEG C) desiccation, it has further been found that with delustering agent A.P. alumina silicate P, A.P. the coating that alumina silicate R, A.P. calcium silicates Q and A.P. magnesium silicates T (being respectively 1i, 2i, 5i and 7i) are prepared, compared with to disappear The coating that photo etching A.P. silica C, silica gel X and silica gel Y (being respectively 9c, 11c and 12c) are prepared, has what is quite improved to do Change the time.Delustering agent A.P. silica A (8i) is than A.P. silica C, silica gel X and silica gel Y (being respectively 9c, 11c and 12c) It shows more to improve.

The touching test method of low temperature desiccation (9 DEG C) confirms the coating that display is prepared with delustering agent A.P. magnesium silicates S (6i) RT results there is most fast drying time, it was demonstrated that during the desiccation slightly a little slower (i.e. without silica) only than bright coating Between.

In the touching test method of low temperature desiccation, it has further been found that with delustering agent A.P. alumina silicate P, A.P. alumina silicate R, A.P. the coating that calcium silicates Q and A.P. magnesium silicates T (being respectively 1i, 2i, 5i and 7i) are prepared, has compared with delustering agent A.P. The coating that silica C, silica gel X and silica gel Y (being respectively 9c, 11c and 12c) are prepared, has the drying time quite improved.

In short, for the results show of coating prepared with drier Oxy-coat such as institute in detail in the claims It is used as the useful part of the silica of traditional high surface area of delustering agent in the delustering agent substitute composition of description, as base In the substitute of the drier of cobalt soap.

In addition to the composition for being not added with delustering agent provides gloss, all desiccation coating all provide sufficiently mute Light.

Embodiment 3

By preparing air curing coating in the base composition as shown in delustering agent is added to in table 5 above Composition, but the difference is that with different drier.In this experiment, will be adopted in the base composition (embodiment 2) of table 5 1101 drier of Borchi Oxy-coat be substituted for Nuodex DryCoat (Rockwood) drier (as described above, 8% kerosin of magnesium chelate).The delustering agent that the addition provided with %w/w is included is shown in the following Table 8.With It is as follows in the delustering agent for preparing air curing paint：

In order to compare, other coating of no delustering agent are prepared.It is measured according to embodiment 2 using B.K. drying machines method of testing The time required to each stage that each coating composition reaches desiccation starts.When measuring the desiccation under low temperature desiccation condition (9 DEG C) Between.Table 8 gives the time reached to composition needed for each desiccation stage.Each coating composition is with used in each example The delustering agent for preparing the coating composition is shown.Coating prepared by other delustering agents useless is shown as " no silica ".It is right In the glossiness of each coating composition as measured using the method described in embodiment 2, it is also contained in table 8 below.

For the low temperature desiccation using B.K. drying machine test methods, using delustering agent A.P. alumina silicate P, A.P. silicon Sour aluminium R, A.P. alumina silicate P W1, A.P. alumina silicate P W2, A.P. calcium silicates Q, A.P. magnesium silicate S and A.P. magnesium silicates T are (respectively For 1i, 2i, 3i, 4i, 5i, 6i and 7i) coating prepared, compared to using delustering agent A.P. silica C, silica gel X and silica gel Y The coating that (being respectively 9c, 11c and 12c) prepares, has the drying time quite improved.

In short, using the results show of the drier DryCoat coating prepared as retouched in detail in the claims It is used as the useful part of traditional high surface area silica of delustering agent in the delustering agent substitute composition stated, as based on cobalt The substitute of the drier of soap.

In addition to the composition of no addition delustering agent provides gloss, all desiccation coating all provide sufficient dumb light.

It should be appreciated that in the case of without prejudice to the scope of the present invention defined in appended claims, The above embodiment can carry out a variety of modifications.

Embodiment that is described above and explaining is considered to be illustrative rather than is only limitted to literal meaning, should It is interpreted as only having shown and described specific embodiment according to the present invention, all changes within the scope of the invention and repair Change, as recorded in appended claims, be construed as in protection domain.It should be understood that in specification Employed in vocabulary such as " preferred ", " preferably ", " preferably " or " more preferable " represent is that its described especially may be used To be preferable, however it must not believe that and such be characterized in necessary and lack these special embodiments and be still believed that It is defined in appended claims in the scope of the present invention.For claims, it is necessary to be intended that, work as vocabulary As " one kind ", "one", " at least one " or " at least a portion " be for drawing feature rather than limiting the claim only There are one such feature, unless especially making opposite explanation in the claims.When use language " at least part " and/or When " part ", article can include point and/or whole article, except non-specifically making opposite explanation.

Claims

1. a kind of curable fluid composition, said composition contain：

A) by oxidation cross-linked curable adhesive,

C) delustering agent,

It is characterized in that, the dry immunomodulator compounds for the transition metal chelate containing ligand and

The delustering agent is：

It is 250m with the surface area measured by BET²The precipitated silica of/below g,

Precipitate metal silicate or

Their mixture.

2. curable fluid composition according to claim 1, wherein, the delustering agent is：

It is 200m with the surface area measured by BET²The precipitated silica of/below g,

Precipitate metal silicate or

Their mixture.

3. curable fluid composition according to claim 1 or 2, wherein, the delustering agent is unbodied precipitation Silica or unbodied precipitation metal silicate.

4. curable fluid composition according to claim 1 or 2, wherein, the delustering agent for metal silicate and It is 450m with the surface area measured by BET²/ below g.

5. curable fluid composition according to claim 4, wherein, the delustering agent is metal silicate and has Surface area by BET measurements is 400m²/ below g.

6. curable fluid composition according to claim 3, wherein, the delustering agent is metal silicate and has Surface area by BET measurements is 450m²/ below g.

7. curable fluid composition according to claim 6, wherein, the delustering agent is metal silicate and has Surface area by BET measurements is 400m²/ below g.

8. curable fluid composition according to claim 4, wherein, the metal silicate has to be measured by BET Surface area be 250m²/ below g.

9. curable fluid composition according to claim 8, wherein, the metal silicate has to be measured by BET Surface area be 200m²/ below g.

10. the curable fluid composition according to any one in claim 5-7, wherein, the metal silicate It is 250m with the surface area measured by BET²/ below g.

11. curable fluid composition according to claim 10, wherein, the metal silicate has to be surveyed by BET The surface area of amount is 200m²/ below g.

12. the curable fluid composition according to any one in claim 1,2,5-9 and 11, wherein, it is described to disappear It is 150m that photo etching, which has by the surface area of BET measurements,²/ below g.

13. according to the curable fluid composition described in claim 3, wherein, the delustering agent has by BET measurements Surface area is 150m²/ below g.

14. according to the curable fluid composition described in claim 4, wherein, the delustering agent has by BET measurements Surface area is 150m²/ below g.

15. according to the curable fluid composition described in claim 10, wherein, the delustering agent has to be measured by BET Surface area be 150m²/ below g.

16. the curable fluid composition according to any one in claim 1,2,5-9,11 and 13-15, wherein, It is 100m that the delustering agent, which has by the surface area of BET measurements,²/ below g.

17. curable fluid composition according to claim 3, wherein, the delustering agent has the table measured by BET Area is 100m²/ below g.

18. curable fluid composition according to claim 4, wherein, the delustering agent has the table measured by BET Area is 100m²/ below g.

19. curable fluid composition according to claim 10, wherein, the delustering agent has by BET measurements Surface area is 100m²/ below g.

20. curable fluid composition according to claim 12, wherein, the delustering agent has by BET measurements Surface area is 100m²/ below g.

21. the curable fluid composition according to any one in claim 1,2,5-9,11,13-15 and 17-20, Wherein, it is 70m that the delustering agent, which has by the surface area of BET measurements,²/ below g.

22. curable fluid composition according to claim 3, wherein, the delustering agent has the table measured by BET Area is 70m²/ below g.

23. curable fluid composition according to claim 4, wherein, the delustering agent has the table measured by BET Area is 70m²/ below g.

24. curable fluid composition according to claim 10, wherein, the delustering agent has by BET measurements Surface area is 70m²/ below g.

25. curable fluid composition according to claim 12, wherein, the delustering agent has by BET measurements Surface area is 70m²/ below g.

26. curable fluid composition according to claim 16, wherein, the delustering agent has by BET measurements Surface area is 70m²/ below g.

27. the curable liquid according to any one in claim 1,2,5-9,11,13-15,17-20 and 22-26 Composition, wherein, the delustering agent is precipitation metal silicate, and wherein metal M is the metal of the 2-13 races of the periodic table of elements In one or more, and M_xO/SiO₂Molar ratio for more than 0.05, wherein, M_xO is metal oxide in precipitated silicate Stoichiometric equation, and x is equal to 2/v, v is the chemical valence of metal.

28. curable fluid composition according to claim 3, wherein, the delustering agent is precipitation metal silicate, Wherein metal M is the one or more in the metal of the 2-13 races of the periodic table of elements, and M_xO/SiO₂Molar ratio for 0.05 with On, wherein, M_xO is the stoichiometric equation of metal oxide in precipitated silicate, and x is equal to 2/v, and v is the chemical valence of metal.

29. curable fluid composition according to claim 4, wherein, the delustering agent is precipitation metal silicate, Wherein metal M is the one or more in the metal of the 2-13 races of the periodic table of elements, and M_xO/SiO₂Molar ratio for 0.05 with On, wherein, M_xO is the stoichiometric equation of metal oxide in precipitated silicate, and x is equal to 2/v, and v is the chemical valence of metal.

30. curable fluid composition according to claim 10, wherein, the delustering agent is precipitation metal metasilicate Salt, wherein metal M are the one or more in the metal of the 2-13 races of the periodic table of elements, and M_xO/SiO₂Molar ratio be More than 0.05, wherein, M_xO is the stoichiometric equation of metal oxide in precipitated silicate, and x is equal to 2/v, and v is the change of metal Conjunction valency.

31. curable fluid composition according to claim 12, wherein, the delustering agent is precipitation metal metasilicate Salt, wherein metal M are the one or more in the metal of the 2-13 races of the periodic table of elements, and M_xO/SiO₂Molar ratio be More than 0.05, wherein, M_xO is the stoichiometric equation of metal oxide in precipitated silicate, and x is equal to 2/v, and v is the change of metal Conjunction valency.

32. curable fluid composition according to claim 16, wherein, the delustering agent is precipitation metal metasilicate Salt, wherein metal M are the one or more in the metal of the 2-13 races of the periodic table of elements, and M_xO/SiO₂Molar ratio be More than 0.05, wherein, M_xO is the stoichiometric equation of metal oxide in precipitated silicate, and x is equal to 2/v, and v is the change of metal Conjunction valency.

33. curable fluid composition according to claim 21, wherein, the delustering agent is precipitation metal metasilicate Salt, wherein metal M are the one or more in the metal of the 2-13 races of the periodic table of elements, and M_xO/SiO₂Molar ratio be More than 0.05, wherein, M_xO is the stoichiometric equation of metal oxide in precipitated silicate, and x is equal to 2/v, and v is the change of metal Conjunction valency.

34. curable fluid composition according to claim 27, wherein, the metal of the metal silicate is selected from Aluminium, calcium, magnesium and their mixtures.

35. curable fluid composition according to claim 34, wherein, the metal of the metal silicate for aluminium or Magnesium.

36. the curable fluid composition according to any one in claim 28-33, wherein, the metal metasilicate The metal of salt is selected from aluminium, calcium, magnesium and their mixtures.

37. curable fluid composition according to claim 36, wherein, the metal of the metal silicate for aluminium or Magnesium.

38. according to the curable fluid composition described in any one in claim 34,35 and 37, wherein, M_xO：SiO₂'s Molar ratio is 0.05-0.6, M_xO is the stoichiometric equation of metal oxide in precipitated silicate, and x is equal to 2/v, and v is the gold The chemical valence of category.

39. curable fluid composition according to claim 36, wherein, M_xO：SiO₂Molar ratio for 0.05-0.6, M_xO is the stoichiometric equation of metal oxide in precipitated silicate, and x is equal to 2/v, and v is the chemical valence of the metal.

40. according to any one in claim 1,2,5-9,11,13-15,17-20,22-26,28-35,37 and 39 Curable fluid composition, wherein, the transition metal of the dry immunomodulator compounds is substantially by iron, manganese or their mixture group Into.

41. curable fluid composition according to claim 3, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

42. curable fluid composition according to claim 4, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

43. curable fluid composition according to claim 10, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

44. curable fluid composition according to claim 12, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

45. curable fluid composition according to claim 16, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

46. curable fluid composition according to claim 21, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

47. curable fluid composition according to claim 27, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

48. curable fluid composition according to claim 36, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

49. the curable fluid composition according to claim 38, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

50. according to any one in claim 1,2,5-9,11,13-15,17-20,22-26,28-35,37,39 and 41-49 The curable fluid composition, wherein, the ligand is selected from bidentate ligand, tridentate ligand, tetradentate ligands, five tooth ligands Or sexadentate ligand or their mixture.

51. curable fluid composition according to claim 3, wherein, the ligand is selected from bidentate ligand, three teeth are matched somebody with somebody Body, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

52. curable fluid composition according to claim 4, wherein, the ligand is selected from bidentate ligand, three teeth are matched somebody with somebody Body, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

53. curable fluid composition according to claim 10, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

54. curable fluid composition according to claim 12, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

55. curable fluid composition according to claim 16, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

56. curable fluid composition according to claim 21, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

57. curable fluid composition according to claim 27, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

58. curable fluid composition according to claim 36, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

59. the curable fluid composition according to claim 38, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

60. curable fluid composition according to claim 40, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

61. appoint according in claim 1,2,5-9,11,13-15,17-20,22-26,28-35,37,39,41-49 and 51-60 Curable fluid composition described in meaning one, wherein, the ligand is for nitrogen ligand.

62. curable fluid composition according to claim 3, wherein, the ligand is for nitrogen ligand.

63. curable fluid composition according to claim 4, wherein, the ligand is for nitrogen ligand.

64. curable fluid composition according to claim 10, wherein, the ligand is for nitrogen ligand.

65. curable fluid composition according to claim 12, wherein, the ligand is for nitrogen ligand.

66. curable fluid composition according to claim 16, wherein, the ligand is for nitrogen ligand.

67. curable fluid composition according to claim 21, wherein, the ligand is for nitrogen ligand.

68. curable fluid composition according to claim 27, wherein, the ligand is for nitrogen ligand.

69. curable fluid composition according to claim 36, wherein, the ligand is for nitrogen ligand.

70. the curable fluid composition according to claim 38, wherein, the ligand is for nitrogen ligand.

71. curable fluid composition according to claim 40, wherein, the ligand is for nitrogen ligand.

72. curable fluid composition according to claim 50, wherein, the ligand is for nitrogen ligand.

73. curable fluid composition according to claim 61, wherein, the ligand be selected from double loop coil ligands, N4Py ligands, TACN ligands, three loop coil ligands, Macrocyclic polyamine ligand or bridge ligand.

74. the curable fluid composition according to any one in claim 62-72, wherein, the ligand is selected from Double loop coil ligands, N4Py ligands, TACN ligands, three loop coil ligands, Macrocyclic polyamine ligand or bridge ligand.

75. according to claim 1,2,5-9,11,13-15,17-20,22-26,28-35,37,39,41-49,51-60 and 62- Curable fluid composition in 73 described in any one, wherein, described adhesive contains the polyunsaturated fatty acid of conjugation Part.

76. curable fluid composition according to claim 3, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

77. curable fluid composition according to claim 4, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

78. curable fluid composition according to claim 10, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

79. curable fluid composition according to claim 12, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

80. curable fluid composition according to claim 16, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

81. curable fluid composition according to claim 21, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

82. curable fluid composition according to claim 27, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

83. curable fluid composition according to claim 36, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

84. the curable fluid composition according to claim 38, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

85. curable fluid composition according to claim 40, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

86. curable fluid composition according to claim 50, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

87. curable fluid composition according to claim 61, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

88. the curable fluid composition according to claim 74, wherein, described adhesive contains more insatiable hungers of conjugation And fatty acid part.

89. a kind of curable fluid composition, which is any one institute in claim 1-39 The curable fluid composition stated, and do not contain the surface area by BET measurements below 0.1 weight % and be more than 250m²/ g's Amorphous silica.

90. a kind of curable fluid composition, which is curable described in claim 89 Fluid composition, and do not contain the surface area by BET measurements below 0.1 weight % and be more than 70m²The amorphous titanium dioxide of/g Silicon；Wherein, it is 70m that delustering agent, which has by the surface area of BET measurements,²/ below g.

91. a kind of curable fluid composition, which is curable described in claim 89 Fluid composition, and the surface area by BET measurements containing below 0.1 weight % is more than 70m²The amorphous silica of/g； It is 70m that delustering agent, which has by the surface area of BET measurements,²/ below g.

92. a kind of curable fluid composition, which is any one institute in claim 1-39 The curable fluid composition stated, and the surface area by BET measurements containing below 0.1 weight % is more than 250m²The nothing of/g Amorphous silicon dioxide.

93. a kind of curable fluid composition, which is curable described in claim 92 Fluid composition, and do not contain the surface area by BET measurements below 0.1 weight % and be more than 70m²The amorphous titanium dioxide of/g Silicon；It is 70m that delustering agent, which has by the surface area of BET measurements,²/ below g.

94. a kind of curable fluid composition, which is curable described in claim 92 Fluid composition, and the surface area by BET measurements containing below 0.1 weight % is more than 70m²The amorphous silica of/g； It is 70m that delustering agent, which has by the surface area of BET measurements,²/ below g.

95. the curable fluid composition according to any one in claim 89-94, wherein, the drier The transition metal of conjunction object contains the cobalt less than 1 weight %.

96. the curable fluid composition according to any one in claim 89-94, wherein, the drier The transition metal for closing object is made of substantially iron, manganese or their mixture.

97. the curable fluid composition according to claim 95, wherein, the transition metal of the dry immunomodulator compounds Substantially it is made of iron, manganese or their mixture.

98. the curable fluid composition according to any one in claim 89-94 and 97, wherein, the ligand Selected from bidentate ligand, tridentate ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

99. the curable fluid composition according to claim 95, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

100. the curable fluid composition according to claim 96, wherein, the ligand is selected from bidentate ligand, three teeth Ligand, tetradentate ligands, five tooth ligands or sexadentate ligand or their mixture.

101. the curable fluid composition according to any one in claim 89-94,97 and 99-100, wherein, The ligand is for nitrogen ligand.

102. the curable fluid composition according to claim 95, wherein, the ligand is for nitrogen ligand.

103. the curable fluid composition according to claim 96, wherein, the ligand is for nitrogen ligand.

104. the curable fluid composition according to claim 98, wherein, the ligand is for nitrogen ligand.

105. the curable fluid composition according to claim 101, wherein, the ligand be selected from double loop coil ligands, N4Py ligands, TACN ligands, three loop coil ligands, Macrocyclic polyamine ligand or bridge ligand.

106. the curable fluid composition according to any one in claim 102-104, wherein, the ligand choosing From double loop coil ligands, N4Py ligands, TACN ligands, three loop coil ligands, Macrocyclic polyamine ligand or bridge ligand.

107. the curable liquid combination according to any one in claim 89-94,97,99-100 and 102-105 Object, wherein, described adhesive contains the polyunsaturated fatty acid part of conjugation.

108. the curable fluid composition according to claim 95, wherein, described adhesive contain conjugation it is more not Saturated fat acid moieties.

109. the curable fluid composition according to claim 96, wherein, described adhesive contain conjugation it is more not Saturated fat acid moieties.

110. the curable fluid composition according to claim 98, wherein, described adhesive contain conjugation it is more not Saturated fat acid moieties.

111. the curable fluid composition according to claim 101, wherein, described adhesive contain conjugation it is more not Saturated fat acid moieties.

112. the curable fluid composition according to claim 106, wherein, described adhesive contain conjugation it is more not Saturated fat acid moieties.

113. a kind of curable fluid composition, which is any one in claim 1-112 The curable fluid composition, wherein, adhesive is alkyd resin.

114. a kind of curable fluid composition, which is any one in claim 1-112 The curable fluid composition, wherein, adhesive contains alkyd resin.

115. the curable fluid composition according to claim 113 or 114, wherein, curable fluid composition For latex paint, solvent-based coating, varnish, wood stain or ink.

Application of the substance below 116. as the delustering agent of curable fluid composition：

Precipitated silica, it is 250m to have by the surface area of BET measurements²/ below g,

Precipitate metal silicate or

Their mixture,

Wherein, the curable fluid composition contains：

By oxidation cross-linked curable adhesive and

Transition metal chelate containing ligand, as the oxidation cross-linked drier chemical combination suitable for being catalyzed described adhesive Object.

117. the application according to claim 116, wherein, precipitated silica is with the surface area by BET measurements 200m²/ below g.

118. the application according to claim 116 or 117, wherein, described adhesive is alkyd resin, and wherein described Curable fluid composition is water based paint, solvent-based coating, varnish, wood stain or ink.

119. the application according to claim 116 or 117, wherein, described adhesive contains alkyd resin, and wherein institute Curable fluid composition is stated as water based paint, solvent-based coating, varnish, wood stain or ink.

120. the application according to claim 116 or 117, wherein, the delustering agent has is by the BET surface areas measured 70m²/ below g, and wherein described curable fluid composition does not contain the surface area measured by BET below 0.1 weight % More than 70m²The amorphous silica of/g.

121. the application according to claim 118, wherein, it is 70m that the delustering agent, which has by the surface area of BET measurements,²/g Hereinafter, and wherein described curable fluid composition do not contain below 0.1 weight % by BET measurement surface area be more than 70m²The amorphous silica of/g.

122. the application according to claim 119, wherein, it is 70m that the delustering agent, which has by the surface area of BET measurements,²/g Hereinafter, and wherein described curable fluid composition do not contain below 0.1 weight % by BET measurement surface area be more than 70m²The amorphous silica of/g.

123. the application according to claim 116 or 117, wherein, the delustering agent has is by the BET surface areas measured 70m²/ below g, and the surface area by BET measurements that wherein described curable fluid composition contains below 0.1 weight % is big In 70m²The amorphous silica of/g.

124. the application according to claim 118, wherein, it is 70m that the delustering agent, which has by the surface area of BET measurements,²/g Hereinafter, and wherein described curable fluid composition contain below 0.1 weight % by BET measurement surface area be more than 70m²The amorphous silica of/g.

125. the application according to claim 119, wherein, it is 70m that the delustering agent, which has by the surface area of BET measurements,²/g Hereinafter, and wherein described curable fluid composition contain below 0.1 weight % by BET measurement surface area be more than 70m²The amorphous silica of/g.

126. according to the application described in any one in claim 116,117,121,122,124 and 125, wherein, it is described to disappear Photo etching is selected from unbodied precipitated silicate aluminium, unbodied precipitated silicate calcium, unbodied precipitated silicate magnesium or theirs is mixed Close object.

127. the application according to claim 118, wherein, the delustering agent is selected from unbodied precipitated silicate aluminium, without fixed The precipitated silicate calcium of shape, unbodied precipitated silicate magnesium or their mixture.

128. the application according to claim 119, wherein, the delustering agent is selected from unbodied precipitated silicate aluminium, without fixed The precipitated silicate calcium of shape, unbodied precipitated silicate magnesium or their mixture.

129. the application according to claim 120, wherein, the delustering agent is selected from unbodied precipitated silicate aluminium, without fixed The precipitated silicate calcium of shape, unbodied precipitated silicate magnesium or their mixture.

130. the application according to claim 125, wherein, the delustering agent is selected from unbodied precipitated silicate aluminium, without fixed The precipitated silicate calcium of shape, unbodied precipitated silicate magnesium or their mixture.

131. the application according to claim 126, wherein, the delustering agent is unbodied precipitated silicate aluminium.

132. according to the application described in any one in claim 127-130, wherein, the delustering agent is unbodied precipitation Alumina silicate.